CN1350565A - Nucleators for crystallizable thermoplastic polymers - Google Patents
Nucleators for crystallizable thermoplastic polymers Download PDFInfo
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- CN1350565A CN1350565A CN99816408A CN99816408A CN1350565A CN 1350565 A CN1350565 A CN 1350565A CN 99816408 A CN99816408 A CN 99816408A CN 99816408 A CN99816408 A CN 99816408A CN 1350565 A CN1350565 A CN 1350565A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/48—Two nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/42—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
- C07C233/43—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of a saturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/57—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C233/62—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
- C07C233/65—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
- C07C233/77—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/80—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C235/56—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C275/40—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C275/42—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
Disclosed are compositions nucleators for crystallizable thermoplastic polymers and, in particular, chemical compounds used as nucleators that comprise moieties that are capable of forming intermolecular hydrogen bonds and that are thermally stable, and the use thereof.
Description
The present invention relates to contain the composition of Nucleators for crystallizable thermoplastic polymers, relate to specifically comprising and to form intermolecular hydrogen bonding and be heat-staple nucleator and application thereof.
Nucleator and finings usually use with crystallizable combinations of thermoplastic polymers in industrial practice, to shorten the process-cycle or to give the physics-chem characteristic of improvement, as various optics and mechanical property, and reduce the contraction of moulded product.About the detailed bill of nucleator and finings can referring to for example United States Patent (USP) 3,367,926 and plastics additive handbook (the 4th edition, Hanser, Munich, 1990, p.863).The metal-salt of the metal-salt that known typical nucleator is aliphatic series or aromatic carboxylic acid in the present technique, aromatics salt, aromatics P contained compound, quinacridone, pigment, have fusing point polymkeric substance, contain the highly-branched polymers (dendroid branching thing) of dendroid branching, and mineral, for example chalk, gypsum, clay, kaolin, mica, talcum and silicate, and their combination (United States Patent (USP) 5,278,216,5,137,973,4,749,736,4,694,064,4,338,228,3,852,237; U.Johnsen and K.-H.Moos:Angew.Makromol.Chem. (application polymer chemistry), the 74th volume, p.1 (1978); A.Wlochowicz and M.Eder: use polymer chemistry, the 171st volume, p.79 (1989); H.N.Beck:J.Appl.Polym.Sci. (journal of applied), the 11st volume, p.673 (1967); F.LBinsbergen:Polymer (polymkeric substance), the 11st volume, p.253 (1970)).In addition, German publication number 1951632 discloses the aromatics carboxylic imide-biphenyl dicarboximide of solid crystal aromatics carboxylic imide-biphenyl dicarboximide and N-replacement.
More recently nucleator of developing and finings are dissolved in (R.Schlotman and R.Walker:Kunststoffe (material), the 86th volume, p.1002 (1996)) in the polymer melt, and this is effective for the dispersion that improves this class additive.The most frequently used will be at last based on the compound of D-sorbyl alcohol, this compounds belongs to total chemical race of carbohydrate, be defined as poly-hydroxy aldehyde, polyhydroxyketone, maybe can be hydrolyzed into compound (R.T.Morrion and the RobertMeilson Boyd: organic chemistry of these compounds, the 2nd edition, (Allyn and Bacon company, Boston), 1966, p.983).Several commercially available nucleators based on sorbyl alcohol are arranged at present, comprise 1,3-2,4-dibenzylidene-D-sorbyl alcohol (Millad 3905, Milliken chemical company), 1,3-2, (4-methylene phenyl)-(Millad 3904 for the D-sorbyl alcohol for 4-two, Milliken chemical company) 1,3-2,4-two (4-ethyl benzylidene)-D-sorbyl alcohol (N-4, Mitsui petroleum industry company).United States Patent (USP) 5,574,174,5,198,484 and WO 95/13317 preparation and the application of glucitol derivative are disclosed.United States Patent (USP) 4,294,747 disclose the polyvalent alcohol acetal of phenyl aldehyde and derivative thereof.United States Patent (USP) 5,216,051 has narrated the many alkylol cpds of three acetals.Sorbitol dibenzal (United States Patent (USP) 4,016,118) and phenyl-phosphate combination of compounds are used and are disclosed in United States Patent (USP) 4,585, in 817.Although the wide range of commercial purposes is arranged, but still exist many with based on the compound of carbohydrate as the nucleator difficulty relevant with finings.The at first preparation of sorb alcohol radical nucleator and refining some trouble.With for example use another relevant well-known difficulty of sorbyl alcohol finings in polyolefin resin is can form small bubbles in the article of being made by this resin, and this small bubbles (United States Patent (USP) 5,198,484) occur with the white point form.At last, other shortcoming is that its temperature stability can not be satisfactory, and unfortunately, this character is the natural characteristics of this material.
Therefore, need a kind of effective nucleator that can be used to improve thermoplastic polymer processing characteristics and physical and chemical performance.
Have now found that some had not only contained the organic compound that can form the intermolecular hydrogen bonding part but also contain the part compatible with thermoplastic polymer is effective nucleator of crystallizable thermoplastic polymer.
Therefore, the present invention relates to a kind of composition, it comprises:
(i) one or more contain the nucleator of the part that can form intermolecular hydrogen bonding; With
(ii) one or more crystallizable thermoplastic polymers, said composition can randomly comprise the filler of additive commonly used.Specifically, the present invention relates to a kind of composition, wherein comprise (i) a kind of crystallizable thermoplastic polymer and the (ii) nucleator shown in one or more following formulas:
Wherein: x is the integer of 2-7; Y is the integer of 0-4; Z is the integer of 0-4; The x+y+z sum equals the integer of 3-7;
M is the integer of 1-3; And wherein A is and part B, B ' or an X ' or a covalently bound center of its combination; Wherein said part B and B ' contain at least 1 unit that can form one or more intermolecular hydrogen bondings; And wherein part X and X ' are compatible with described crystallizable thermoplastic polymer; And wherein X is covalently bound to B.
Another aspect of the present invention relates to by a kind of crystallizable thermoplastic polymer and a kind ofly contains the composition that the part that can form intermolecular hydrogen bonding and the part compatible with crystallizable thermoplastic polymer are formed.
Another aspect of the present invention relates to the composition of being made up of a kind of crystallizable thermoplastic polymer and a kind of nucleator, said composition is characterised in that, when its crystallization peak temperature when melt cools off higher at least 3 ℃ than the pure-crystallization peak temperature of thermoplastic polymer that do not contain nucleator.
Another aspect of the present invention relates to the composition of being made up of a kind of crystallizable thermoplastic polymer and a kind of nucleator, said composition is characterised in that, when the size of spherulite this crystalline polymer when melt cools off less than 50% pure crystallization thermoplastic polymer in the size of spherulite.
Another aspect again of the present invention relates to the composition of being made up of a kind of crystallizable thermoplastic polymer and one or more nucleators, and said composition is compared with pure crystallization thermoplastic polymer has lower mist degree.
A further aspect of the invention relates to the composition of being made up of a kind of crystallizable thermoplastic polymer and one or more nucleators, and said composition has the thermostability of raising.
The present invention also has an aspect to relate to a kind of novel method that improves crystallizable melt of thermoplastic polymers crystallization rate again, and this method comprises in described melt and adds the nucleator of the present invention of significant quantity, and relates to the product according to this novel method manufacturing.
Last aspect of the present invention provides the product of being made by the crystallizable thermoplastic polymer of the nucleator of the present invention that comprises significant quantity.
Advantage provided by the present invention comprises the process period that reduces crystallizable thermoplastic polymer.In addition, the feature of the polymkeric substance that forms according to the present invention is relatively to have improved heat, light and/or mechanical property.Other purposes of the present invention, advantage and new characteristics will propose in back to back description part, and a part will become very clear for the insider when the following content of check, perhaps can sharpen understanding by implementing the present invention.Objects and advantages of the present invention can realize with combination by the means that particularly point out in the claims and obtain.
Also can understand the present invention more fully in conjunction with the accompanying drawings by following detailed, and make further advantage of the present invention become very clear.In the accompanying drawing:
Fig. 1 is the light micrograph that does not contain the isotactic polyprophlene film of nucleator.This film is to carry out compression molding at 210 ℃, obtains with 10 ℃/minute speed cooling and 104 ℃ of crystallizations subsequently.Magnification is 120 times.
Fig. 2 is the light micrograph that contains the isotactic polyprophlene film of 0.75% weight nucleator three (3,4-two (oxygen base in the last of the ten Heavenly stems) phenylene-carbonyl amino-1,4-phenylene) the amine Compound I-1 of table 1 (below be also referred to as).This film is to carry out compression molding at 210 ℃, obtains with 10 ℃/minute speed cooling and 104 ℃ of crystallizations subsequently.Magnification is 120 times.
Fig. 3 has described thermogravimetric analysis (TGA) record that under the nitrogen Compound I in the his-and-hers watches 1-5 (3) and I-7 (2) and Millad 3988 (1) carry out, and shows according to compound of the present invention to have higher thermostability.
Nucleator
Have general formula as follows according to Nucleators for crystallizable thermoplastic polymers of the present invention:
Wherein:
X is the integer of 2-7;
Y is the integer of 0-4;
Z is the integer of 0-4;
The x+y+z sum equals the integer of 3-7;
M is the integer of 1-3;
In the formula (1), A is a center covalently bound with part B, B ' or X ' or its combination; Wherein said part B and B ' contain at least 1 list that can form one or more intermolecular hydrogen bondings Unit; And wherein part X and X ' are compatible with described crystallizable thermoplastic polymer; And X wherein Covalently bound to B. The effect of core A provides a plurality of part B of a kind of connection, B ' Or the means of X ' and combination thereof, these parts are conducive to form induces this crystallizable thermoplasticity polymerization The structure of thing nucleation.
According to the present invention, the preferred nucleator that crystallizable thermoplastic polymer is used is those compounds shown in the general formula (1), wherein:
X is the integer of 3-6;
Y is the integer of 0-3;
Z is the integer of 0-2;
The x+y+z sum equals the integer of 3-7;
M is 1 or 2 integer.
According to the present invention, in the preferred nucleator, those compounds shown in the general formula (1) more preferably, wherein:
X is the integer of 3-4;
Y is the integer of 0-2;
Z is 0 or 1 integer;
The x+y+z sum equals the integer of 3-6;
M is 1 or 2 integer.
According to the present invention, the most preferred nucleator that crystallizable thermoplastic polymer is used has general formula (1), wherein:
X is 3;
Y is the integer of 0-2;
Z is 0 or 1 integer;
The x+y+z sum equals the integer of 3-6;
M is 1 or 2 integer.
The representational part that can be used as nucleator of the present invention center A is carbon, nitrogen, phosphorus, boron and silicon, can connect or not connect one or more aromatics, cyclic aliphatic, aliphatic series, alkene, alkynes, diene, ether, thioether or ketone chain link on it, and their combination; Do not have to replace and have 4,5,6 or 7 yuan of aromatics and the cyclic aliphatic monocyclic carbocyclic ring and the fused iso of replacement, this ring can comprise one or more heteroatomss, as nitrogen, sulphur and oxygen and combination thereof, and can connect or not connect one or more aromatics, cyclic aliphatic, aliphatic series, alkene, alkynes, diene, ether, thioether or ketone chain link on it, and their combination.
Preferred part is carbon and nitrogen, can connect on it or not connect one or more aromatics, cyclic aliphatic or-(CH
2)
p-chain link, and combination, wherein p is 1 or 2; Do not have to replace and have 5 or 6 yuan of aromatics and the cyclic aliphatic monocyclic carbocyclic ring and the fused iso of replacement, this ring can comprise one or more heteroatomss, as nitrogen, sulphur and oxygen and combination thereof, and can connect on it or not connect one or more aromatics, cyclic aliphatic or-(CH
2)
p-chain link, and combination, wherein p is 1 or 2.
In these preferred parts, preferred part is carbon and nitrogen, is connected with one or more aromatics or cyclic aliphatic chain link and combination thereof on it; Do not have to replace or have 6 yuan of aromatics and the cyclic aliphatic monocyclic carbocyclic ring and the fused iso of replacement, this ring can comprise one or more nitrogen-atoms, can connect on it or not connect one or more aromatics, cyclic aliphatic or-(CH
2)
p-chain link, and combination, wherein p is 1 or 2.
In the preferred part that can be used as nucleator of the present invention center A, most preferably can be with or without the following array structure of replacement:
Part B in the nucleator of the present invention and B ' are the sort of parts as the part of nucleator molecule that can form one or more intermolecular hydrogen bondings between the nucleator molecule.Hereinafter hydrogen bond is defined as because hydrogen atom and little strong electronegative element such as fluorine, oxygen and the nitrogen of atomic radius, and on lesser extent, electrostatic interaction between chlorine and the sulphur and a kind of key (Lehrbuch der Organischen Chemie (organic chemistry textbook), the H.Beyer that form; Hirzel, the Stuttgart, 1976, p.105,106).The effect of part B and B ' is the formation of inducing and control the structure that helps crystallizable thermoplastic polymer nucleation, and makes it stable.
The illustrative example of part B that can be identical or different when at every turn occurring is that those contain persons such as ester, thioesters, ether, thioether, ketone, secondary amine and tertiary amine, acid amides, imide, imines, azo, azoxy, urea, carbamate, thiocarbamate and sulphonamide.
Preferred part B that can be identical or different when at every turn occurring is that those contain one or more and are selected from the following units person: acid amides, imide, imines, urea, carbamate, thiocarbamate, sulphonamide etc.In these preferred parts, preferred part B that can be identical or different when at every turn occurring is that those contain one or more and are selected from the following units person: acid amides, imide and sulphonamide.Especially preferred is those persons of containing the amide units.
The illustrative example of part B ' that can be identical or different when at every turn occurring is that those contain acid as part persons such as carboxylic acid and sulfonic acid, alcohol, phenol, mercaptan, amine, ethanamide, cyano group and hydrazines.
Comprise part X and X ' according to Nucleators for crystallizable thermoplastic polymers of the present invention, its effect is to make this nucleator compatible with crystallizable thermoplastic polymer and help nucleator to be dispersed in the crystallizable thermoplastic polymer.Therefore, the selection of crystallizable thermoplastic polymer is depended in the selection of the concrete chemical property of part X and X '.Generally speaking, contain the nucleator combinations of thermoplastic polymers use bigger of polarity part X and X ' with the polarity that contains polar group.The nucleator that contains less part X of polarity and X ' then with only contain only a few or combinations of thermoplastic polymers that polarity of polar functionalities is not little and use.Usually, part X and X ' can be chirality or be not chirality, can be identical or different when occurring, and be selected from following one group: H, respectively contains about 20 carbon atoms of 1-at straight chain and branched-alkyl, alkenyl, alkoxyl group, alkanoyl, alkylthio, alkylthio alkyl at every turn; The alkaryl of straight chain and branching, aralkyl, alkyl sulfinyl, alkoxyalkyl, alkane alkylsulfonyl, carbalkoxy, carboxylic acid, wherein alkyl or alkoxyl group respectively contain about 20 carbon atoms of 1-; By the alkyl that contains about 20 carbon atoms of 1-of one or more sulfonic acid, carboxylic acid, halogen, nitro, cyano group, tetrazo or epoxy moieties replacement; 3,4,5,6 or 7 yuan of aromatics and alicyclic monocyclic carbocyclic ring and fused iso that one or more substituting groups and unsubstituted are arranged; this ring can comprise heteroatomss such as one or more nitrogen, sulphur, sulfinyl, sulphonyl or oxygen, for example thienyl, pyrryl, furyl, pyridyl or its combination.
The of the present invention most preferred specific embodiments that contains nucleator is selected from following one group: center: A substituting group
Center: A substituting group
Center: A substituting group
As the explanation of its use and further guidance, also the note according to general formula (1) has provided said structure.Preferably, above-mentioned nucleator and low-pole or nonpolar crystallizable thermoplastic polymer use as isotactic polyprophlene and copolymer in combination thereof.
Nucleator of the present invention has according to its concrete structure and changes very wide thermal characteristics, as fusing point.For being used to implement the present invention, this nucleator preferably has a solidification value, promptly forms the temperature as a result that molecule aggregates or solid temperature or temperature range equal or exceed the crystallizable thermoplastic polymer that does not contain nucleator of the present invention in fusion or dissolved nucleator.
The structure that the present invention will get rid of especially is those based on carbohydrate or contains the structure of saccharide unit, for example sorbyl alcohol and derivative thereof.This structure is normally known, and has the limited shortcoming of thermostability, therefore, is restricted during especially as nucleator of the crystallizable thermoplastic polymer that requires high processing temperature usually with high-melting-point or softening temperature or finings.In contrast to this, have high decomposition temperature, typically be higher than 230 ℃ according to composition of the present invention.
Some compound of general structure (1) is on the books in prior art." the preparation method of the equal benzene trimethamides of three stearyl (trimesamide) (chemical communication, volume 7, p.575 (1996)) that for example, people such as Yasuda have described N, N ', N.Also described 4,4 ', 4 " three (stearyl amino) triphenylamines (Y.Yasuda, Y.Takebe, M.Fukumoto, H.Inada and Y.Shirota, Adv.Mat. (material progress), volume 8, p.740 (1996)).But this compound and crystallizable combinations of thermoplastic polymers are used in also unexposed so far or suggestion, and particularly the nucleator as crystallizable thermoplastic polymer uses.
The amount that joins the nucleator of the present invention in the crystallizable thermoplastic polymer is one " significant quantity ".By employed here, " significant quantity " is meant is enough to make the crystallization peak temperature of polymkeric substance to improve at least 3 ℃ of required amounts.This amount is equivalent to the amount of traditional nucleator usually.In preferred specific embodiments of the present invention, the amount of used nucleator is about 20% weight of about 0.005-of total polymer weight in the composition, in particularly preferred specific embodiments of the present invention, the consumption of nucleator is about 10% weight of about 0.005-of above-mentioned gross weight.In these particularly preferred specific embodiments, most preferably the consumption of nucleator is those embodiments of about 5% weight of about 0.005-of total polymer weight in the present composition.
The present composition is characterised in that the size of polymer crystals spherolite in the thermoplastic polymer composition is typically less than 50% pure crystallization thermoplastic polymer, the spherulite size that does not promptly contain the crystallization thermoplastic polymer of nucleator of the present invention, therefore, consequently the former compares with the latter by a kind of composition, has lower mist degree.
Crystallizable thermoplastic polymer
The kind that is used to implement crystallizable thermoplastic polymer of the present invention is a lot, therefore can select according to the concrete end-use of the product that contains the present composition.Can be used for crystallizable thermoplastic polymer of the present invention and comprise normally used all thermoplastic polymers and multipolymer in the plastics.Useful crystallizable thermoplastic homopolymer or multipolymer are polyolefine, as polyethylene, tactic polypropylene, ethylene-propylene copolymer, Stereoregular Styrene Polymers, polynorbornene, polyisobutene, poly-(1-butylene), poly-(3-methyl-1-butene), poly-(1-amylene), poly-(4-methyl-1-pentene), poly-(1-hexene), poly-(5-methyl isophthalic acid-hexene), poly-(2-methyl styrene), poly-(4-methoxy styrene) etc., and their multipolymer; Aromatics or aliphatic poly oxide, for example polyoxymethylene, polyethylene oxide, polybutylene oxide, poly(propylene oxide), polyphenylene oxide, polysulphide such as polypropylene sulfide, polyphenylene sulfide etc., and polymkeric substance; Aromatics, aliphatic series and araliphatic polymeric amide are as nylon 6, nylon 12, nylon 6,6, nylon 6,10 etc.; Aromatics, aliphatic series and araliphatic polyester are as polyethylene terephthalate, polybutylene terephthalate, PEN, polyvinyl alcohol and polycarbonate.
Except above-mentioned main ingredient, composition of the present invention also can randomly comprise binder component commonly used in a kind or multiple other thermoplastic resin.This optional component comprises filler, toughener, softening agent, dispersing auxiliary, impact modifying agent, chain extension agent, tinting material, releasing agent, metal inactivator, antioxidant, photostabilizer, lubricant, static inhibitor, fire retardant, white dyes, biostat, chemical foaming agent, linking agent and other nucleator.These optional components are that the insider is familiar with, and are described in standard textbook and the handbook, as plastics additive handbook (the 4th edition, Hanser, Munich, 1990).
Composition of the present invention can adopt traditional compounding means by main component and other optional components are carried out blend or mix preparing as far as possible equably.The compounding means that are fit to are the means of knowing in the present technique as extrusion molding, blend at intermittence etc., have therefore just repeated no more here.In addition, all components or part component can be made into masterbatch or carry out pre-blend in melt or in the solvent of suitably selecting.
Composition of the present invention is specially adapted to produce transparency and mechanical property and the film of making, fiber, container, coating, part, diaphragm, bar, tubing, fabric and the foams etc. with improvement in short period.Therefore, the invention further relates to a kind of method that improves crystallizable thermoplastic polymer crystallization velocity, this method comprises that a kind of adding about 20% weight of about 0.001-or multiple nucleator are to produce above-mentioned molded article.
In specific embodiments, composition of the present invention comprises following combination: a kind or multiple polyolefine, as the following nucleator of polyethylene, tactic polypropylene and ethylene-propylene copolymer and a kind or multiple general formula (1), wherein:
I) center A is the single atom that is selected from nitrogen and phosphorus; Or A is 15 or 6 yuan of heterocyclic aromatics or non-aromatic monocyclic or condensed ring that do not have to replace or have replacement, and this ring comprises carbon atom and one or more atom or its combinations as nitrogen, sulphur or oxygen; With
Ii) identical and comprise the part B of acid amides or urea when occurring at every turn; Or it is different and comprise at least 2 acid amides and at least 1 part B that is selected from the part of ester and urea when occurring at every turn; Or it is different and comprise at least 2 ureas and at least 1 part B that is selected from the part of ester and acid amides when occurring at every turn;
Iii) x is 3; Y is 0 or 1 integer; Z is 0 or 1 integer; M is 1 or 2 integer.
Embodiment
The compound of general formula (1) can be used the own known method described in the document (for example in research on standard, as the organic chemistry method of Houben-Weyl, the Georg Thieme of Stuttgart publishes), prepares under known condition.Carrying out these whens reaction, also can adopt specifically do not mention here but known preferred supplementary condition itself.If necessary, initial substance also can original position form, and will they not separate from reaction mixture, but they further are reacted in formula (1) compound.
Relevant compound of the present invention illustrates with the following examples.Provided the fusing point m.p. of all cpds among the embodiment.In context, percentage ratio by weight; All temperature are degree centigrade ℃ to provide." conventional aftertreatment " is meant: add water, leach throw out, with organic solvent extraction and/or by crystallization and/or chromatography refined products.
Embodiment A:
4.05g (10.2mmol) 3,4-two octyloxy Benzoyl chlorides and the anhydrous LiCl of 0.5g join under inert atmosphere in anhydrous NMP of 50ml and the 5ml anhydrous pyridine, and are cooled to 5 ℃.Add 0.99g (3.4mmol) three (the amino phenylene of 4-) amine.Reaction mixture is heated to 75 ℃.After 2 hours reaction mixture is joined in the 500ml distilled water.Leach throw out.After conventional aftertreatment, obtain three (3,4-two (octyloxy) phenylene-carbonyl imino--1,4-phenylene) amine (table 1, No.I-7), m.p:229 ℃.
Prepared following compounds similarly:
Three (3,4-two (oxygen base in the last of the ten Heavenly stems) phenylene-carbonyl imino--1,4-phenylene) amine (Compound I-1), m.p:211 ℃;
Three (3,4-two (oxygen base in the ninth of the ten Heavenly Stems) phenylene-carbonyl imino--1,4-phenylene) amine (Compound I-2), m.p:219 ℃;
Three (3,4,5-three (oxyethyl group) phenylene-carbonyl imino--1,4-phenylene) amine (Compound I-3), m.p:258 ℃;
Three (cyclopentyl-carbonyl imino--1,4-phenylene) amine (Compound I-4), m.p:270 ℃;
Three (cyclohexyl-carbonyl imino--1,4-phenylene) amine (Compound I-5), m.p:276 ℃;
Three (3-cyclohexyl propylidene-carbonyl imino--1,4-phenylene) amine (Compound I-6), m.p:238 ℃;
Three (cyclohexylmethylene-carbonyl imino--1,4-phenylene) amine (Compound I-8), m.p:335 ℃;
Three (phenylcarbonyl group imino--1,4-phenylene) amine (Compound I-9), m.p:198 ℃;
Embodiment B:
1.76g (12.0mmol) the anhydrous LiCl of hexanaphthene carboxyl acyl chloride and 0.5g joins under inert atmosphere in anhydrous NMP of 50ml and the 5ml anhydrous pyridine, and is cooled to 5 ℃.Add 0.40g (3.0mmol) 2,4,6-triamino toluene.Reaction mixture is heated to 75 ℃.After 2 hours reaction mixture is joined in the 500ml distilled water.Leach throw out.After conventional aftertreatment, obtain 2,4, and 6-(hexanaphthene carbonyl imino-) toluene (Table I, No.II-1), m.p.:199 ℃.
Embodiment C:
1.75g (10.0mmol) the anhydrous LiCl of 4-cyclohexyl aniline and 0.5g joins under inert atmosphere in anhydrous NMP of 50ml and the 5ml anhydrous pyridine, and is cooled to 5 ℃.Add 0.80g (3.0mmol) 1,3,5-benzene three formyls.Reaction mixture is heated to 75 ℃.After 2 hours reaction mixture is joined in the 500ml distilled water.Leach throw out.After conventional aftertreatment, obtain 1,3, and 5-(cyclohexyl-1,4-phenylene imino-carbonyl) benzene (Table I, No.III-2), m.p.:317 ℃.
Prepared following compounds similarly:
1,3,5-(4-tertiary butyl phenylene imino-carbonyl) benzene (compound III-1), m.p.358 ℃;
1,3,5-(4-hexyloxy phenylene imino-carbonyl) benzene (compound III-3), m.p.80 ℃;
1,3,5-(normal-butyl imino-carbon back) benzene (compound III-4), m.p.:219 ℃;
1,3,5-(phenylimino carbonyl) benzene (compound III-5), m.p.:311 ℃.
Embodiment D:
3.00g (10.3mmol) three (the amino phenylene of 4-) amine and the anhydrous LiCl of 0.1g join under inert atmosphere in anhydrous NMP of 70ml and the 10ml anhydrous pyridine, and are cooled to 5 ℃.Add 4.30g (36.2mmol) phenylcarbimide.Reaction mixture is heated to 75 ℃.After 2 hours reaction mixture is joined in the 400ml cold distilled water.Leach throw out.After conventional aftertreatment, obtain three (phenylimino carbonyl imino--1,4-phenylene) amine (Table I, No.IV-1), m.p.:278 ℃.
Compound below having prepared similarly:
Three (cyclohexyl imino-carbonyl imino--1,4-phenylene) amine (compound-IV-2), m.p.:230 ℃.
Embodiment E:
1.89g (15.0mmol) 2,4,6-triamino-1,3,5-triazines and 35ml triethylamine join 130ml under inert atmosphere anhydrous 1, in the 4-diox, and is cooled to 5 ℃.Add 9.28g (60.0mmol) 3-methyl benzoyl chloride.Reaction mixture heated 3 hours under refluxing.Reaction mixture is cooled to room temperature, joins then in the 600ml cold distilled water.Leach throw out, drying.After conventional aftertreatment, obtain three (3-methylphenylene carbonyl imino-)-1,3,5-triazines.(Table I, No.V-1), m.p.:227 ℃.
Compound below having prepared similarly:
Three (phenylcarbonyl group imino-)-1,3,5-triazines (compound V-2), m.p.:277 ℃.
Embodiment F:
1.89g (15.0mmol) 2,4-diamino-6-hydroxy pyrimidine and the anhydrous LiCl of 0.1g join under inert atmosphere in anhydrous NMP of 130ml and the 25ml anhydrous pyridine, and are cooled to 5 ℃.Add 8.06g (55.0mmol) hexanaphthene carboxyl acyl chloride.Reaction mixture is heated to 75 ℃.After 2 hours reaction mixture is joined in the 400ml cold distilled water.Leach throw out.After conventional aftertreatment, obtain 2,4-two (cyclohexyl-carbonyl imino-)-6-(cyclohexyl carbonyl oxygen base) pyrimidine.(Table I, No.VI), m.p.:225 ℃.
Embodiment G:
1.40g (5.8mmol) 3,5-diaminobenzoic acid-4-aminomethyl phenyl ester joins under inert atmosphere in anhydrous NMP of 30ml and the 1.3ml anhydrous pyridine, and is cooled to 5 ℃.Add 2.16g (14.0mmol) phenyllacetyl chloride.Reaction mixture is heated to 90 ℃.After 2 hours reaction mixture is joined in the 400ml cold distilled water.Leach throw out.After conventional aftertreatment, obtain 3,5-two (benzyloxycarbonyl group imino-) phenylformic acid-4-aminomethyl phenyl ester.(Table I, No.VII), m.p.:212 ℃.
Embodiment H:
1.5g (9.8mmol) 3,5-diaminobenzoic acid-3,5-3,5-dimethylphenyl acid amides joins under inert atmosphere among the anhydrous NMP of 30ml, and is cooled to 5 ℃.Add 2.70g (21.6mmol) NSC 87419.Reaction mixture is heated to 75 ℃.4.5 after hour reaction mixture is joined in the 300ml cold distilled water.Leach throw out.After conventional aftertreatment, obtain 3,5-two (cyclohexyl imino-carbonyl imino-) phenylformic acid-3,5-3,5-dimethylphenyl-acid amides.(Table I, No.VIII), m.p.:295 ℃.
I. general procedure
A. combination process A
About 20mg (1% weight) powder additive joins in the powdery isotactic polyprophlene of about 2g, refluxes about 1 hour at 120 ℃ in the flask that 100ml p-Xylol (Aldrich chemical company) is housed then.Then this flask is cooled to room temperature.Mixture further cools off with liquid nitrogen, and lyophilize under vacuum and room temperature obtains the powdered polypropylene additive agent mixture.Carry out same processing with virgin pp in addition and obtain control sample.
B. combination process B-1
About 50mg (1% weight) powder additive joins in about 4.95g powdery isotactic polyprophlene (Aldrich chemical company), and rotary drum mixes the back and grinds in mortar.With a part of mixture heating up to 22 ℃, keep about 5-10 minute, but except indicating in addition, be cooled to room temperature then.In addition polypropylene is similarly handled separately with preparation blank sample.Unless point out in addition, otherwise the add-on of additive is 1% weight.
B. combination process B-2
In 59.91g powdery isotactic polyprophlene (Aldrich chemical company), or in the multipolymer (ELF-Atochem (FR) Cedex 22, 94091 Paris La Defense, France) that contains the isotactic polyprophlene of small amount of ethylene comonomer, adding 90mg powder additive (0.15% weight), rotary drum mixed 24 hours in Glass Containers then.Part mixture about 10 minutes time of blend in 230 ℃ small test chamber twin screw circulation extrusion machine, collect in room temperature then.In addition, similarly handle with preparation blank sample with polypropylene separately.
C. dsc (DSC)
Finish drilling that the Perkin-Elmer DSC instrument (model DSC7) done is analyzed various mixtures according to standard program and in the same old way crystallization behavior with one in dry nitrogen atmosphere.About 5-10mg sample is enclosed in the aluminium cup, be heated to 230 ℃ from 130 ℃, kept 5 minutes, be cooled to 50 ℃ with 10 ℃/minute speed subsequently at 220 ℃ with 10 ℃/minute speed.The data that are expressed as crystallization peak temperature (Tc) are peak temperatures of heat release in the thermogram that records when cooling.
D. thermogravimetric analysis (TGA)
Thermostability with a selected sample of automation of operation Netzsch TGA instrument (STA 409) analysis in nitrogen.About 10mg sample is put in the alumina crucible, be heated to 640 ℃ with 10 ℃/minute speed from 50 ℃ then.
E. opticmicroscope
By carrying out compression molding at 210 ℃, cool off with 10 ℃/minute speed subsequently, make selected sample thereby form film from melt.Check these samples with polarizing microscope (Leitz Laborlux 12-pol) under the Nicol crossed in transmitted light then.
II. embodiment explanation
Embodiment 1
Three (3,4-two (oxygen base in the last of the ten Heavenly stems) phenylene-carbonyl imino--1,4-phenylene) amine (Compound I in the table 1-1) (1% weight) mixes with combination process A with polypropylene.Virgin pp is to all analyze with dsc with mixture in the same old way.The crystallization peak temperature of mixture is than pure high 12.4 ℃ in the same old way.
Hereinafter, mixture of the present invention with the difference of both Tcs is in the same old way represented the Δ T=12.4 of present embodiment ℃ with Δ T.
Embodiment 2
Compound I in the table 1-6 (1% weight) is mixed with combination process B with polypropylene.Virgin pp is to all analyze with dsc with mixture in the same old way.ΔT＝13.0℃。
Embodiment 3
Repeat embodiment 1 and 2, with blending means A (Compound I-1 and I-2) or method B (B1: Compound I-3, I-6, I-8, I-9, II-1, III-1, III-2, III-3, III-4 and III-5; B2: Compound I-4, I-5, I-7, IV-1, IV-2, V-1, V-2, VI, VII and VIII) all cpds is mixed with polypropylene.Following table 1 has been compiled the result that the DSC method records.Table 1:No. center: T[℃ of A substituting group Δ] polypropylene is not to have 0,0 in the same old way
Table 1 (continuing): No. center: T[℃ of A substituting group Δ]
Table 1 (continuing): No. center: T[℃ of A substituting group Δ]
Table 1 (continuing): No. center: T[℃ of A substituting group Δ]
Table 1 (continuing): No. center: T[℃ of A substituting group Δ]
Table II: No. center: T[℃ of A substituting group Δ] polypropylene/ethylene
There is not 0,0 pair in the same old way
Embodiment 4
210 ℃ compression molded pure, do not contain the polypropylene of nucleator and contain three (3 of 1% weight, 4-two (oxygen base in the last of the ten Heavenly stems) phenylene-carbonyl imino--1, the 4-phenylene) film of amine (Compound I in the table 1-1) cools off with 10 ℃/minute speed subsequently, and 104 ℃ of crystallizations.Fig. 1 is the polyacrylic light micrograph that does not contain nucleator.Fig. 2 is the light micrograph that contains the isotactic polyprophlene of 1% weight Compound I-1.The magnification of these 2 Photomicrographs is identical, both comparison shows that 50% also much smaller than virgin pp control film spherulite size of the spherulite size of the polypropylene screen that contains additive, this is the symbol of additive nucleation ability, also is the reason that the former mist degree reduces.
Embodiment 5
Compound I under nitrogen in the his-and-hers watches 1-5 (curve 3) and I-7 (curve 2) and Millad 3988 (curve 1) carry out thermogravimetric analysis (TGA).Fig. 3 has drawn these compounds TGA curve separately, shows the thermally-stabilised height of The compounds of this invention.
Claims (12)
1. composition wherein comprises (i) a kind of crystallizable thermoplastic polymer and the (ii) nucleator shown in one or more following formulas:
Wherein:
X is the integer of 2-7;
Y is the integer of 0-4;
Z is the integer of 0-4;
The x+y+z sum equals the integer of 3-7;
M is the integer of 1-3; And wherein A is and part B, B ' or an X ' or a covalently bound center of its combination; Wherein said part B and B ' contain at least 1 unit that can form one or more intermolecular hydrogen bondings; And wherein part X and X ' are compatible with described crystallizable thermoplastic polymer; And wherein X is covalently bound to B.
2. according to the composition of claim 1, this group that wherein said center A selects free carbon, nitrogen, phosphorus, boron and silicon to form, they can be replaced by one or more aromatics, cyclic aliphatic, aliphatic series, alkene, alkynes, diene, ether, thioether or ketone chain link and combination thereof, connect thereon; Or there be not 4,5,6 or 7 yuan of aromatics and cyclic aliphatic monocyclic carbocyclic ring and the fused iso that replaces and replacement is arranged, this ring can comprise one or more heteroatomss, as nitrogen, sulphur and oxygen and combination thereof, they can be replaced by one or more aromatics, cyclic aliphatic, aliphatic series, alkene, alkynes, diene, ether, thioether or ketone chain link and combination thereof.
3. according to the composition of claim 1 or 2, wherein said part B can be identical or different when occurring at every turn, and contain one or more and be selected from following unit: ester, thioesters, ether, thioether, ketone, secondary amine and tertiary amine, acid amides, imide, imines, azo, azoxy, urea, carbamate, thiocarbamate and sulphonamide.
4. according to any one composition among the claim 1-3, wherein said part B ' can be identical or different when occurring at every turn, and be selected from this group part that contains one or more carboxylic acids and sulfonic acid, alcohol, phenol, mercaptan, amine, ethanamide, cyano group and diazanyl group.
5. according to any one composition among the claim 1-4, wherein said part X and X ' can be chirality or be not chirality, can be identical or different when occurring at every turn, and be selected from following one group: H, respectively contains 1-20 carbon atom at straight chain and branched-alkyl, alkenyl, alkoxyl group, alkanoyl, alkylthio, alkylthio alkyl; The alkaryl of straight chain and branching, aralkyl, alkyl sulfinyl, alkoxyalkyl, alkane alkylsulfonyl, carbalkoxy, carboxylic acid, wherein alkyl or alkoxyl group respectively contain 1-20 carbon atom; By the alkyl that contains 1-20 carbon atom of one or more sulfonic acid, carboxylic acid, halogen, nitro, cyano group, tetrazo or epoxy moieties replacement; 3,4,5,6 or 7 yuan of aromatics and the alicyclic monocyclic carbocyclic ring and the fused iso of one or more substituting groups and unsubstituted are arranged, and this ring can comprise heteroatoms or its combination of one or more nitrogen, sulphur, sulfinyl, sulphonyl or oxygen.
6. according to any one composition among the claim 1-5, wherein said composition is characterised in that: its crystalline peak temperature is higher at least 3 ℃ than the crystallization peak temperature of described crystallizable thermoplastic polymer.
7. according to any one composition among the claim 1-6, wherein said composition is characterised in that: the size of polymer crystals spherolite is less than 50% size that does not contain spherulite in the pure crystallization thermoplastic polymer of described nucleator in the described composition.
8. method that improves crystallizable thermoplastic polymer crystallization rate, this method comprise a kind of adding about 0.001%～about 20% weight or multiple as according to the nucleator of any one definition among the claim 1-6.
9. comprise the formed article according to the composition of any one among the claim 1-7, wherein said article are selected from film, fiber, container, coating, part, diaphragm, bar, tubing, fabric and foams.
10. the compound shown in the following general formula
Wherein A, B, B ', X, X ', m, x, y and z such as claim 1 definition; Wherein A has triphenylamine replacement or that do not have replacement; Wherein B comprises amide units; And wherein y and z equal 0, but compound 4,4 ', 4 " except three (stearyl amino) triphenylamine.
11. the purposes of the nucleator of using as crystallizable thermoplastic polymer as formula (1) compound of any one definition among the claim 1-5.
12. a thermoplastic polymer composition wherein comprises:
A) one or more polyolefine are selected from following one group: polyethylene, tactic polypropylene and ethylene-propylene copolymer; With
B) nucleator of one or more general formulas (1), wherein:
I) center A is the single atom that is selected from nitrogen and phosphorus; Or A is 15 or 6 yuan of heterocyclic aromatics or non-aromatic monocyclic or condensed ring that do not have to replace or have replacement, and this ring comprises carbon atom and one or more atom or its combinations as nitrogen, sulphur or oxygen; With
Ii) identical and comprise the part B of acid amides or urea when occurring at every turn; Or it is different and comprise at least 2 acid amides and at least 1 part B that is selected from the part of ester and urea when occurring at every turn; Or it is different and comprise at least 2 ureas and at least 1 part B that is selected from the part of ester and acid amides when occurring at every turn;
Iii) x is 3; Y is 0 or 1 integer; Z is 0 or 1 integer; M is 1 or 2 integer.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP1999/001429 WO2000052089A1 (en) | 1999-03-05 | 1999-03-05 | Nucleators for crystallizable thermoplastic polymers |
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| CN1350565A true CN1350565A (en) | 2002-05-22 |
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| CN99816408A Pending CN1350565A (en) | 1999-03-05 | 1999-03-05 | Nucleators for crystallizable thermoplastic polymers |
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| EP (1) | EP1179032A1 (en) |
| JP (1) | JP2002538255A (en) |
| KR (1) | KR20020010578A (en) |
| CN (1) | CN1350565A (en) |
| AU (1) | AU3328599A (en) |
| BR (1) | BR9917195A (en) |
| CA (1) | CA2364504A1 (en) |
| MX (1) | MXPA01008864A (en) |
| NO (1) | NO20014294L (en) |
| WO (1) | WO2000052089A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113861058A (en) * | 2021-09-18 | 2021-12-31 | 北京理工大学 | Triamido methylbenzene nucleating agent, preparation method and use method |
| CN113979888A (en) * | 2021-09-18 | 2022-01-28 | 北京理工大学 | Method for preparing N, N, N-trineovalerylated-1, 3, 5-triaminobenzene |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100820125B1 (en) | 2000-12-06 | 2008-04-08 | 시바 스폐셜티 케미칼스 홀딩 인코포레이티드 | Trimesic acid derivatives and mixtures thereof |
| BR0209814A (en) * | 2001-05-17 | 2004-06-01 | Milliken & Co | Low shrinkage, braided polypropylene fibers produced from these, and methods of manufacture thereof |
| KR100943687B1 (en) * | 2002-05-30 | 2010-02-23 | 시바 홀딩 인코포레이티드 | -crystalline polypropylenes |
| BRPI0415479A (en) * | 2003-10-17 | 2006-12-26 | New Japan Chem Co Ltd | amide based compound, polyolefin resin composition and molded product |
| CN101155776B (en) | 2005-04-07 | 2011-05-04 | 新日本理化株式会社 | Process for producing tricarboxylic acid tris(alkyl-substituted cyclohexylamide) |
| ES2352579T3 (en) * | 2006-05-16 | 2011-02-21 | Basf Se | MONO AND MULTICAPA BLOWED FILMS. |
| WO2010104628A1 (en) * | 2009-03-12 | 2010-09-16 | Exxonmobil Chemical Patents Inc. | Polyolefin masterbatches and films |
| US8492468B2 (en) | 2010-06-04 | 2013-07-23 | Sumitomo Chemical Company, Limited | Polypropylene resin composition |
| US9580575B2 (en) * | 2013-09-23 | 2017-02-28 | Milliken & Company | Polyethylene articles |
| JP7094887B2 (en) * | 2016-03-09 | 2022-07-04 | ミリケン・アンド・カンパニー | Trisamide compound and composition containing it |
| JP7260271B2 (en) * | 2018-09-21 | 2023-04-18 | 保土谷化学工業株式会社 | Nucleating agent, resin composition containing said nucleating agent, and molded article containing said resin composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3367926A (en) * | 1964-03-25 | 1968-02-06 | Dow Chemical Co | Modification of crystalline structure of crystallizable high polymers |
| US4294747A (en) * | 1979-09-24 | 1981-10-13 | Milliken Research Corporation | Shapeable thermoplastic resin composition containing cyclic acetal |
| JPS60252655A (en) * | 1984-05-28 | 1985-12-13 | Mitsubishi Petrochem Co Ltd | Polyphenylene ether composition having improved moldability |
| DE3884002T2 (en) * | 1987-02-07 | 1994-04-21 | Idemitsu Petrochemical Co | Glass fiber reinforced polyolefin composition. |
| US5278216A (en) * | 1989-04-18 | 1994-01-11 | Mitsui Toatsu Chemicals, Incorporated | Syndiotactic polypropylene resin composition |
| US6417294B1 (en) * | 1995-12-21 | 2002-07-09 | Mitsui Chemicals, Inc. | Films and molded articles formed from aliphatic polyester compositions containing nucleating agents |
| US5780545A (en) * | 1996-03-08 | 1998-07-14 | Eastman Kodak Company | Stable release agents |
-
1999
- 1999-03-05 MX MXPA01008864A patent/MXPA01008864A/en not_active Application Discontinuation
- 1999-03-05 CA CA002364504A patent/CA2364504A1/en not_active Abandoned
- 1999-03-05 BR BR9917195-3A patent/BR9917195A/en not_active Application Discontinuation
- 1999-03-05 AU AU33285/99A patent/AU3328599A/en not_active Abandoned
- 1999-03-05 EP EP99914479A patent/EP1179032A1/en not_active Withdrawn
- 1999-03-05 CN CN99816408A patent/CN1350565A/en active Pending
- 1999-03-05 KR KR1020017011217A patent/KR20020010578A/en not_active Application Discontinuation
- 1999-03-05 WO PCT/EP1999/001429 patent/WO2000052089A1/en not_active Application Discontinuation
- 1999-03-05 JP JP2000602710A patent/JP2002538255A/en active Pending
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2001
- 2001-09-04 NO NO20014294A patent/NO20014294L/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113861058A (en) * | 2021-09-18 | 2021-12-31 | 北京理工大学 | Triamido methylbenzene nucleating agent, preparation method and use method |
| CN113979888A (en) * | 2021-09-18 | 2022-01-28 | 北京理工大学 | Method for preparing N, N, N-trineovalerylated-1, 3, 5-triaminobenzene |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9917195A (en) | 2001-12-26 |
| CA2364504A1 (en) | 2000-09-08 |
| NO20014294D0 (en) | 2001-09-04 |
| NO20014294L (en) | 2001-10-25 |
| WO2000052089A1 (en) | 2000-09-08 |
| JP2002538255A (en) | 2002-11-12 |
| MXPA01008864A (en) | 2002-10-23 |
| EP1179032A1 (en) | 2002-02-13 |
| AU3328599A (en) | 2000-09-21 |
| KR20020010578A (en) | 2002-02-04 |
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